|Publication number||US7901730 B2|
|Application number||US 11/113,537|
|Publication date||Mar 8, 2011|
|Filing date||Apr 25, 2005|
|Priority date||Apr 26, 2004|
|Also published as||US20050238895|
|Publication number||11113537, 113537, US 7901730 B2, US 7901730B2, US-B2-7901730, US7901730 B2, US7901730B2|
|Inventors||Lonnie G. Johnson, Davorin Babic|
|Original Assignee||Johnson Research & Development Co., Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (38), Referenced by (1), Classifications (27), Legal Events (3)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This claims benefit of provisional of U.S. Patent Application Ser. No. 60/565,305 filed Apr. 26, 2004.
This invention relates generally to electrolytes, and more particularly to ceramic electrolytes.
The present invention relates to proton conducting electrolytes which are prepared for use in intermediate temperature range fuel cells and other electrochemical devices that operate in the temperature range of between 200° C. to 600° C.
Proton conducting electrolytes are a core component of any electrochemical device based on proton conduction such as, for example, fuel cells, hydrogen separation and pumping devices, etc. It is well known that presently there are no proton conducting material with proton conductivity high enough to successfully operate in the intermediate temperature range (200-600° C.) when prepared by current material preparation techniques that result in an electrolyte layer at least 10 μm thick. The polymer based electrolytes, such as Nafion or PBI, are know to operate in a temperature of below 200° C., as a temperature above such destroys the polymer electrolyte. Perovskite ceramic electrolytes such as zirconates and cerates must operate at very high temperatures as their conductivities are not high enough until the temperature reaches approximately 600° C. Hence, no suitable electrolyte is found for the intermediate temperature range of between 200° C. and 600° C.
However, it is desirous to develop an electrolyte which may operate within the intermediate temperature range as it solves many outstanding problems of lower temperature systems, especially fuel cells, while avoiding high operating temperature induced mechanical and thermal mismatch problems. It thus is seen that a need remains for an intermediate temperature electrolyte and a method of producing such which overcomes problems associated with those of the prior art. Accordingly, it is to the provision of such that the present invention is primarily directed.
In a preferred form of the invention, a thin film proton conducting electrolyte comprises a nanoporous supporting substrate, and a ceramic layer positioned upon the porous supporting substrate stack, the ceramic layer having a thickness less than or equal to 2 microns.
In another preferred form of the invention, a method of manufacturing a proton conducting electrolyte comprises the steps of (a) providing a nanoporous supporting substrate, (b) filling the nanopores of the nanoporous supporting substrate with a filler material, and (c) depositing a ceramic layer upon the filled nanoporous supporting substrate.
With reference next to the drawings, there is shown in a method of producing a ceramic proton conducting electrolyte assembly 10 for use in intermediate temperature range devices, such as fuel cells, hydrogen separation and pumping devices, and other electrochemical devices.
The electrolyte assembly 10 includes a nanoporous supporting substrate 11, a temporary substrate pore filler material 12, and a ceramic electrolyte layer 13 positioned upon the substrate 11. The nanoporous substrate 11 may be made of a copper layer produced in accordance with the teachings of U.S. Patent Application Ser. No. 10/918,250, now U.S. Pat. No. 6,986,838, which is commonly owned and specifically incorporated herein by reference. The substrate pore filler material 12 may be a photoresist or polymer material, such as AZ P4620 made by Clariant or Microposit S 1813 made by Shipley. The ceramic electrolyte layer 13 is preferable a yttrium doped strontium zerconate (Y:SrZrO3), but may also be barium zerconate, strontium cerate, barium cerate, or other proton conductive perovskite ceramic materials.
The electrolyte assembly 10 is preferable manufactured in the following manner. An approximately 10 micron layer of porous copper substrate 11 is produced or otherwise provided having a pore size of approximately 200 nm, as shown in
Once the nanoporous substrate 11 is produced, the pores 14 are filled with a pore filler material 12 to provide the substrate 11 with a smooth and uniform top surface 15, as shown in
Once the electrolyte layer 13 is deposited the pore filler material 12 is removed by an appropriate solvent, such as acetone or an alcohol, as shown in
It should be understood that other dopants may be used as an alternative to the yttrium, such as indium, neodymium, scandium, or other similar material. It should also be understood that other material may be utilized to produce the substrate 11 as an alternative to the copper disclosed in the preferred embodiment. It should be understood that it is believed that the pore filler material 12 should be removed from the pores 14. However, should an very high proton conducting material is utilized or discovered it may be conceivable that the filler material need not be removed.
It thus is seen that a proton conducting electrolyte for use with intermediate temperature fuel cells or other electrochemical devices is now provided which overcomes problems associated with those of the prior art. It should of course be understood that many modifications may be made to the specific preferred embodiment described herein without departure from the spirit and scope of the invention as set forth in the following claims.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US4040410||Jun 14, 1976||Aug 9, 1977||Allied Chemical Corporation||Thermal energy storage systems employing metal hydrides|
|US4049877||Sep 17, 1975||Sep 20, 1977||Ford Motor Company||Thermoelectric generator|
|US4098958||Jul 7, 1977||Jul 4, 1978||Ford Motor Company||Thermoelectric generator devices and methods|
|US4422500||Dec 23, 1981||Dec 27, 1983||Sekisui Kagaku Kogyo Kabushiki Kaisha||Metal hydride heat pump|
|US4523635||Jul 30, 1982||Jun 18, 1985||Sekisui Kagaku Kogyo Kabushiki Kaisha||Metal hydride heat pump system|
|US4562511||Jun 30, 1983||Dec 31, 1985||Matsushita Electric Industrial Co., Ltd.||Electric double layer capacitor|
|US4677038||Oct 29, 1984||Jun 30, 1987||Temple University Of The Commonwealth System Of Higher Education||Gas concentration cells for utilizing energy|
|US4692390||Aug 18, 1986||Sep 8, 1987||General Electric Company||Method and system for hydrogen thermal-electrochemical conversion|
|US4781029||Jun 5, 1987||Nov 1, 1988||Hydride Technologies Incorporated||Methods and apparatus for ocean thermal energy conversion using metal hydride heat exchangers|
|US4818638||Jun 9, 1987||Apr 4, 1989||General Electric Company||System for hydrogen thermal-electrochemical conversion|
|US5139895||Jul 19, 1991||Aug 18, 1992||General Electric Company||Hydrogen thermal electrochemical converter|
|US5306577||Jul 15, 1992||Apr 26, 1994||Rockwell International Corporation||Regenerative fuel cell system|
|US5336573||Jul 20, 1993||Aug 9, 1994||W. R. Grace & Co.-Conn.||Battery separator|
|US5436091||Nov 22, 1993||Jul 25, 1995||Valence Technology, Inc.||Solid state electrochemical cell having microroughened current collector|
|US5498489||Apr 14, 1995||Mar 12, 1996||Dasgupta; Sankar||Rechargeable non-aqueous lithium battery having stacked electrochemical cells|
|US5532074||Jun 27, 1994||Jul 2, 1996||Ergenics, Inc.||Segmented hydride battery|
|US5540741||Jan 17, 1995||Jul 30, 1996||Bell Communications Research, Inc.||Lithium secondary battery extraction method|
|US5547782||Mar 13, 1995||Aug 20, 1996||Dasgupta; Sankar||Current collector for lithium ion battery|
|US5571634||Aug 3, 1995||Nov 5, 1996||Bell Communications Research, Inc.||Hybrid lithium-ion battery polymer matrix compositions|
|US5584893||Nov 17, 1995||Dec 17, 1996||Valence Technology, Inc.||Method of preparing electrodes for an electrochemical cell|
|US5588971||Oct 19, 1994||Dec 31, 1996||Arthur D. Little, Inc.||Current collector device and method of manufacturing same|
|US5591544||Mar 6, 1995||Jan 7, 1997||Arthur D. Little, Inc.||Current collector device|
|US5597659||Oct 7, 1994||Jan 28, 1997||Matsushita Electric Industrial Co., Ltd.||Manufacturing method of a separator for a lithium secondary battery and an organic electrolyte lithium secondary battery using the same separator|
|US5778515||Apr 11, 1997||Jul 14, 1998||Valence Technology, Inc.||Methods of fabricating electrochemical cells|
|US5928436||Feb 26, 1997||Jul 27, 1999||Advanced Modular Power Systems, Inc.||Means for controlling thermal properties of AMTEC cells|
|US6033796||Feb 3, 1998||Mar 7, 2000||Baji; Yasuo||Chemical reaction battery|
|US6368383 *||Jun 7, 2000||Apr 9, 2002||Praxair Technology, Inc.||Method of separating oxygen with the use of composite ceramic membranes|
|US6899967||Jun 10, 2002||May 31, 2005||Excellatron Solid State, Llc||Electrochemical conversion system|
|US7033637 *||Jan 12, 2000||Apr 25, 2006||Microcoating Technologies, Inc.||Epitaxial thin films|
|US20020012824||Oct 9, 2001||Jan 31, 2002||Johnson Lonnie G.||Electrochemical conversion system|
|US20020020298 *||Jul 26, 2001||Feb 21, 2002||Ernst Drost||Supported metal membrane, a process for its preparation and use|
|US20020064692||Dec 31, 2001||May 30, 2002||Johnson Lonnie G.||Electrochemical conversion system|
|US20050013933 *||Jun 10, 2004||Jan 20, 2005||Hancun Chen||Method of forming ion transport membrane composite structure|
|EP0055855A2||Dec 28, 1981||Jul 14, 1982||Sekisui Kagaku Kogyo Kabushiki Kaisha||Metal hydride heat pump|
|EP0071271A2||Jul 29, 1982||Feb 9, 1983||Sekisui Kagaku Kogyo Kabushiki Kaisha||Metal hydride heat pump system|
|EP0168062A2||Dec 28, 1981||Jan 15, 1986||Sekisui Kagaku Kogyo Kabushiki Kaisha||Metal hydride heat pump assembly|
|GB1357347A *||Title not available|
|JPS58147575A *||Title not available|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US9005486||Apr 7, 2011||Apr 14, 2015||Savannah River Nuclear Solutions, Llc||Proton conducting ceramics in membrane separations|
|U.S. Classification||427/115, 427/372.2|
|International Classification||H01B1/08, B05D5/12, C23C30/00, B32B15/04, B32B9/00, H01B1/12, C23C26/00, C23C28/00, B05D3/02|
|Cooperative Classification||H01B1/122, C23C26/00, H01M8/1253, H01M8/1246, C23C30/00, Y02E60/525, H01B1/08, H01M8/1016, Y02P70/56|
|European Classification||C23C26/00, H01B1/08, H01M8/10E, C23C30/00, H01M8/12E2B, H01B1/12F, H01M8/12E2|
|Apr 25, 2005||AS||Assignment|
Owner name: JOHNSON RESEARCH & DEVELOPMENT CO., INC., GEORGIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:JOHNSON, LONNIE G.;BABIC, DAVORIN;REEL/FRAME:016503/0662
Effective date: 20050425
|Sep 22, 2014||FPAY||Fee payment|
Year of fee payment: 4
|Sep 22, 2014||SULP||Surcharge for late payment|